Data Set (knb-lter-sbc.93.10)

Records of moored SeaFET pH, SeaBird CTD and oxygen at Anacapa, Santa Cruz and San Miguel Islands, California from 2012-2015

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These methods, instrumentation and/or protocols apply to all data in this dataset:

Protocols and/or Procedures
Description:

Sites and sensor deployments

SeaFET pH sensors (Martz et al. 2010) and Conductivity, Temperature, Depth, and Oxygen sensors (CTDO sensors, Sea-Bird Electronics 37-SMP-ODO MicroCAT C-T-ODO (P) Recorder) were deployed at three sites along the northern Channel Islands: (1) Anacapa Island Landing Cove pier (ALC, 34° 00.985’N, 119° 21.724’W) in a marine reserve with kelp forest habitat, (2) Santa Cruz Island Prisoner’s Harbor pier (PRZ, 34° 01.225’N, 119° 41.057’W) surrounded by a large shallow eelgrass bed (Zostera pacifica), and (3) San Miguel Island northern subtidal mooring (SMN, 34° 03.417’N, 120° 20.731’W) at 6 m in open water over a sandy bottom at 18 m depth (Fig. 1). Sensors at ALC and PRZ were deployed at 3 - 4 m depth and less than 1 m from the benthos on a pier piling.

In May 2013, CTDO sensors were deployed in addition to pH sensors at ALC and PRZ. CTDO sensors were actively pumped through an anti-fouling passage and temperature, salinity, pressure, and dissolved oxygen were recorded every 15 min. In August 2013, the sensor array from PRZ was moved to SMN for a one-year overlapping period of data collection with ALC. At each site, sensors were swapped every 2 - 3 months. SeaFET sensor surfaces did not exhibit biofouling upon recoveries.

Data processing

Calibration samples for SeaFET sensors were collected 1 – 8 times during each 2 - 3 month deployment via SCUBA, free diving, or a GO-FLOW (General Oceanics) bottle drop from the pier following Standard Operating Procedures (SOP) 1 (Dickson et al. 2007). Multiple calibration samples were taken to quantify spatio-temporal mismatch of the sensor data and bottle sample (Bresnahan et al. 2014). Samples were fixed immediately with saturated mercuric chloride. Water samples were analyzed for pH25 °C (SOP 6b, using m-cresol purple from Sigma-Aldrich®), total alkalinity (SOP 3b, using open-cell titrator Mettler-Toledo T50) (Dickson et al. 2007), and salinity (YSI 3100 Conductivity Instrument) when no corresponding salinity measurements was available from a CTDO sensor. In-situ pHT (total hydrogen ion scale) was calculated using either temperature recorded by the SeaFET or CTDO sensor when available (CO2Calc (Robbins et al. 2010); CO2 constants from (Dickson and Millero 1987; Mehrbach et al. 1973)). All pH data are reported as pHT (“SF_pHint_tot”).

SeaFET data processing followed methods from (Bresnahan et al. 2014) for single and multiple calibration samples using Matlab (R2012b, R2014a). When SeaFET deployments were paired with CTDO sensors (May 2013 – September 2014), temperature data from the CTDO sensors was used to correct for the offset associated with the uncalibrated SeaFET thermistor. CTDO sensors underwent factory calibration at the start and end of the project. Sensors were rinsed with DI water and dilute Triton-X, between deployments. CTDO data was interpolated onto the SeaFET sampling period and all data are reported in Coordinated Universal Time, unless specified otherwise. One 24-hour gap of CTDO data was interpolated to match the deployment length of the pH sensor at ALC when necessary for computations. Rare instances where pH declined to below pH 7.7, within two observations and independent of changes in temperature, were removed for quality control. Oxygen saturation recorded by the CTDO sensor was converted to dissolved oxygen (DO) μmol kg-1 using the oxygen solubility combined fit conversion equation from (García and Gordon 1992).

Error estimates

Post-calibration of CTDO sensors revealed negligible drifts in oxygen, salinity, and temperature. A total of six in-situ water samples were collected for Winkler determination for dissolved oxygen (Wetzel and Likens 1991) and showed a mean 0.9 +/- 0.9 % positive offset from sensor observations (maximum offset was 2.4 %). Post-calibration indicated oxygen sensor drift of less than 1-2 % across the three instruments. The data were not corrected for drift of the oxygen sensor and accuracy for this data is +/- 2 %. A small drift in conductivity resulted in a salinity accuracy of +/- 0.02 psu, and temperature drift was less than 0.001 degree C for all sensors with a reported accuracy of +/- 0.002 °C. Data were not corrected for sensor drift.

Errors in pHT measurement are largely due to the use of unpurified m-cresol dye (0.02, (Liu et al. 2011)), user error (+/1 0.006, (Kapsenberg et al. 2015)), and spatio-temporal mismatch of the calibration sample as determined from multiple calibration samples in one deployment (+/- 0.010 for SMN, ± 0.026 for PRZ, +/- 0.005 for ALC). The resultant estimated standard uncertainty of pH data differed by site and was +/1 0.023 (SMN), +/- 0.033 (PRZ), and +/- 0.022 (ALC).

References

Bresnahan, P. J., T. R. Martz, Y. Takeshita, K. S. Johnson, and M. Lashomb. 2014. Best practices for autonomous measurement of seawater pH with the Honeywell Durafet. Methods Oceangr. 9: 44-60.

Dickson, A. G., and F. J. Millero. 1987. A comparison of the equilibrium constants for the dissociation of carbonic acid in seawater media. Deep-Sea Res. I 34: 1733-1743.

Dickson, A. G., C. L. Sabine, and J. R. Christian. 2007. Guide to best practices for ocean CO2 measurements. PICES Special Publication 3: 191 pp.

García, H. E., and L. I. Gordon. 1992. Oxygen solubility in seawater: better fitting equations. Limnol. Oceanogr. 37: 1307-1312.

Kahru, M., R. M. Kudela, M. Manzano-Sarabia, and B. G. Mitchell. 2012. Trends in the surface chlorophyll of the California Current: merging data from multiple ocean color satellites. Deep Sea Research Part II: Topical Studies in Oceanography 77: 89-98.

Kapsenberg, L., A. L. Kelley, E. C. Shaw, T. R. Martz, and G. E. Hofmann. 2015. Near-shore Antarctic pH variability has implications for biological adaptation to ocean acidification. Sci. Rep. 5.

Liu, X., M. C. Patsavas, and R. H. Byrne. 2011. Purification and characterization of meta-cresol purple for spectrophotometric seawater pH measurements. Environ. Sci. Technol. 45: 4862-4868.

Martz, T. R., J. G. Connery, and K. S. Johnson. 2010. Testing the Honeywell Durafet® for seawater pH applications. Limnol. Oceanogr. Methods 8: 172-184.

Mehrbach, C., C. H. Culberso, J. E. Hawley, and R. M. Pytkowic. 1973. Measurement of apparent dissociation constants of carbonic acid in seawater at atmospheric pressure. Limnol. Oceanogr. 18: 897-907.

Otero, M. P., and D. Siegel. 2004. Spatial and temporal characteristics of sediment plumes and phytoplankton blooms in the Santa Barbara Channel. Deep Sea Research Part II: Topical Studies in Oceanography 51: 1129-1149.

Reum, J. C. and others 2015. Interpretation and design of ocean acidification experiments in upwelling systems in the context of carbonate chemistry co-variation with temperature and oxygen. ICES J. Mar. Sci.

Robbins, L. L., M. E. Hansen, J. A. Kleypas, and S. C. Meylan. 2010. CO2calc—A user-friendly seawater carbon calculator for Windows, Max OS X, and iOS (iPhone). U.S. Geological Survey Open-File Report 2010–1280.

Wetzel, R. G., and G. E. Likens. 1991. Limnological Analyses: Second Edition. Springer-Verlag New York, Inc.